JPS59133295A - Liquid fuel based on powdered solid fuel, petroleum residue and water, manufacture and application thereof in boiler or industrial furnace - Google Patents

Abstract

A fluid fuel mixture is formed of a suspension of a pulverized solid fuel and of at least one aqueous phase representing from 15 to 40 percent of the mixture before an optional incorporation of an additive. The mixture can comprise, as a supplement to particle-size fractions of the pulverized solid fuel, or as a replacement for some of these fractions, additional particle-size fractions produced from heavy petroleum residues of a natural or synthetic origin which are solid at the temperature at which the invention is practiced. The fluid fuel mixture may be used, for example, in boilers, industrial furnaces, or gasification reactors.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to powdered solid fuels such as pulverized coal or of petroleum origin, liquid fuels based on petroleum residues and water, and processes for their production.

Currently, with the aim of reducing consumption of petroleum hydrocarbons in particular,
Much research has been done to increase the overall use of coal as a fuel.

On the one hand, due to the inherent disadvantages of traditional coal utilization (difficulties in handling, transportation, storage, feeding, removal of combustion residues, pollution, etc.), on the other hand, the commonly used combustion equipment Solving the aforementioned problems has proven particularly difficult because the technology environment is unique to liquid fuels and not suitable for solid fuels7.

For these reasons, pulverized coal is mixed with a suitable liquid or liquid.
The realization of a solid fuel composition suspended in an 8-molecular fuel was investigated.

However, the realization of such compositions is fraught with a number of problems, especially the stability of the composition and the carbon content.

Today in the trenches, these closely interconnected issues are
Only compromise solutions emerged that were insufficient to compete with liquid hydrocarbons.

In fact, the stability (sedimentability) of a pulverized coal suspension depends on the physical properties of the liquid (density, viscosity, etc.), as well as the mass of the coal in the liquid and the size of the pulverized coal particles.

Therefore, in many cases, the stability of the suspension is worse as the chi of the coal is lower and the particle size of the aged pulverized coal is larger.

In this case, the production of pulverized coal requires expensive equipment and relatively high costs.

In other cases, the converted coal has an excessive ash content. The use of coal as a fuel requires a deashing operation before its use, and the coal particles resulting from such operations are too small (due to the nature of coal) to produce liquid fuels with high carbon content. Generally, 100% of the particles are 40 microns or less, 30
microns or less, or 15 microns or less). This remarkable increase in the amount of carbon can only be achieved by adding lime with a larger grain size in known methods, but the ash content of this large grain coal is naturally high. Become. This is because the smaller the particle size, the more insufficient the removal of ash becomes.

Furthermore, bright liquid in the suspension exhibits the following disadvantages:

If the liquid is water, the flammability of the suspension is significantly affected by this and the thermal efficiency is reduced. Therefore, it is necessary to extract a portion of the water immediately before the boiler, which may lead to a significant decline in the economic balance.

If the liquid used is fuel oil, the cost of this liquid greatly reduces the profitability and advantages of this method.

In this regard, a composition containing pulverized coal of 40 microns or less, water, and a dispersant? ! French Patent No. 2,393,053 proposes that if this mixture is transported, for example by pumping in a lightning conductor, a carbon content of up to about 40% is suitable from the point of view of its viscosity. states that.

In addition, “La Rivista dei Cowl
Austibili” magazine, (1981), 35. Tiger 9
, p. 385-394 describes studies of dispersing pulverized coal into fuel liquids, such as fuel oil in oil-water emulsions.

This paper states that a low concentration (on the order of 30 wt.) dispersion of powdered coal in oil behaves as a Newtonian fluid. The viscosity increases gradually for solid contents above 30 inches, and increases rapidly at contents between 40 inches and 50%.

This article states that by adding powdered coal to an oil-water emulsion, a stable suspension that behaves as an oil is obtained. 50 parts of powdered coal with a diameter of 70 microns or less;
Best results were obtained with 30 parts oil and 20 parts water.

In order to increase the amount of carbon in the powdered coal/water suspension, with or without the addition of additives, while remaining within the appropriate viscosity range, ultrafine powdered coal (less than 10 microns) and coarser powdered coal can be used. (20-2oo microns) powdered coal and 111'5
An admixture of water with additives was proposed.

In this regard, European Patent No. EP-0052412 alludes to a number of examples of obtaining suspensions containing 63% coal which are stable over time and show no tendency to sedimentation.

From these examples it follows that the proposed suspensions exhibit a relatively high liquid content or require the use of a particular particle size of coal. In practice, when it is necessary to produce fine or ultra-fine powder coal, the fuel user faces a difficult coal grinding problem, and the humidity of this grinding is very low.
The milling cost is low, so the crushing cost is low. Additionally, if a fuel mixture has to be produced from deashed coal with a particle size of less than 20 microns as a result of the deashing operation, fuel users run into the problem of the concentration of coal in the liquid mix I.
These problems can only be solved by adding expensive additives or pulverized coal of a certain particle size with high ash content, which therefore deprives the mixture of advantages.

The purpose of the present invention is to eliminate these disadvantages.

To this end, the present invention provides a form of suspension of a powdered solid fuel, such as a product derived from mineral ore proboscis carbon or petroleum heavy residues, in an aqueous phase, optionally with at least one additive. In liquid fuels, the particle size composition of solid fuel powders resulting from crushing, screening operations or deashing operations is determined by the particle size composition of products resulting from solid, heavy petroleum distillation residues at storage temperatures ( The addition of fractions was changed by i, and the aqueous phase was 15 to -10 t@% k of the liquid fuel.
The purpose is to produce a liquid fuel that can be made into a liquid fuel.

More specifically, these additional particle size fractions can be a) directly produced in some industrial cracking units of petroleum feedstocks, or b) alternatively obtained by pulverization of petroleum residues; The pulverization is carried out cold, in Hl, by mechanical comminution, or hot, on the liquid phase residue, and this comminution step is assisted by a gas (e.g. by air or steam) to form the finely divided particles. is then subjected to rapid cooling (water cooling, also air quenching), C) or obtained by emulsification of petroleum heavy residues (mechanical-r-emulsification with optional additives V). In this case, the emulsion obtained can be mixed directly with pulverized coal. By grinding or mechanically emulsifying a solid petroleum residue at a temperature of about 135° C., such as VC in water at 65° C., with optional additives when operating at virtually normal pressure, and then cooling this mixture. Solid petroleum residues (e.g. blown bitumen as an option)
It is possible to produce a dispersion system (ultrafine particles with a particle size on the order of 5 microns) in a liquid.

The method proposed by the present invention has many advantages as follows.

This method allows for very precise control over the particle size of the material added to the pulverized coal, and in many cases the shape factor of that particle, making it possible to scale a stable suspension with a high fuel material content. enable.

This method reduces the grinding cost and the investment in the grinder.

This method can reduce the total percentage of fuel ash.

This method allows the reuse of heavy petroleum residues that have traditionally been a burden to refineries.

This method is effective for both the boiler and its environment.
All existing technologies can be used.

Finally, in the case of compositions of petroleum products with particle sizes larger than ultra-fine deashed coals, the advantages inherent in this type of fuel can be exploited. That is, overall low ash content (deashed coal and petroleum products containing little or no ash), low sulfur content (coal has a normal sulfur content, but deashing removes about half of that sulfur content). ), a product with a high calorific value is obtained.

Furthermore, since the ash remaining in the coal has a size that is about the size of particles that fly out together with the combustion gas, the problem of ash agitation in the furnace is difficult to solve in plants operated with fuel that does not contain any ash. The problem is transferred to the problem of ash recovery in flue gas. Ash recovery from flue gas in this type of plant can be easily achieved using known means (filters, Zyclone, precipitation methods, etc.).

Regarding the petroleum products that can be used in the solid fuel-water suspension according to the invention, these products consist of:

a) Bitumen, oxidized bitumen, residues of deasphalt distillation, residues of atmospheric distillation, residues of vacuum distillation, vis-breaking, catalytic cracking, if these products intervene in the form of emulsions; coking or (ri hydrocracking residues, b) where petroleum products intervene in the form of crushed solids, asphaltenes, hydrocracking, coke from catalytic cranking or coking, combustion residues, gasification residues, heat Decomposition residues, residues of deasphalt distillation, non-limiting examples of liquid-liquid production embodiments according to the present invention are all described below.

In the case of mixtures in which VC petroleum residues are interposed to provide a deficient particle size fraction or a supplementary particle size fraction in the solid-water fuel mixture, this fraction can be ashed as specified in -F.

a) Ultrafine fraction (less than 20 microns). In this case, finely powdered petroleum residues, such as residues from deasphalting distillation, or bituminous emulsions are used;
(compared to the desired ratio of conventionally pulverized pulverized coal (80%
(80% below microns) and add water. The final mixture in this case consists of 50% stone, 50% stone, 50%
It will contain 0-30% solid fuel, additional water, and optional additives and stabilizing additives. Part of this additional water can also be replaced, in a manner known per se, by an organic solvent such as an alcohol, in particular methanol or ethanol.

b) Intermediate fraction, e.g. 7 from 20 to 80 microns
Luxion. In this case, the petroleum residue may desirably consist of distillation residue or petroleum coke.

C) coarse fraction. In this case, in order to introduce a relatively fine blue solid fuel into a solid-water fuel mixture containing only 50 parts, coarse particles of, for example, 80 to 120 microns are crushed (in other words, all of the emulsion-like distillation residue is used). I can do it.

Therefore, the retardation fractions described in a, b, and c above change the particle size composition of powdered solid fuels such as natural coal, washed coal-like slime, or products generated from petroleum subsoil residues and proboscises. 1 can be done.

In addition, the additional fractions described under b+c are particularly suitable for the production of improved "solid-water" fuels in which the coal fraction consists of ultra-fine demineralized coal powder.

It is possible to remove petroleum residue particles (particle size less than 5 microns) from water by crushing and emulsifying the oil residue in the water. These particles are ultrafine in a large amount of solid-water fuel suspension, l+1i
1 (deficiency) particle size fraction is desirable.

The second and third examples relate to suspensions obtained by adding powdered coal to a petroleum distillation residue-water emulsion.

Example 1 According to this example, the suspension consisted of 60 tons of petroleum distillation residue, water, a Binturu type additive manufactured by Vercules, and an insulin type additive manufactured by Westonco. ,
The pH of the emulsion is on the order of 12-14. Add pulverized coal to this emulsion, add 80% of this pulverized coal (can contain 36.7% pulverized coal, and pump the final product containing 75.68% of fuel material). It is confirmed that it is possible.

Even with the addition of Romardo D additive, the results obtained are comparable, with demulsification in this case occurring at a powdered coal content of 39.73%.

Example 2 In this example, the suspension consists of pulverized coal, 80% by weight of which has a particle size of less than 80 microns, and a cationic emulsion, in which the emulsion is composed of 1r 160 parts of petroleum residue distillate and 40 parts of water. -Polyram S-hydrochloric acid mixture.

When containing 35% pulverized coal, the product obtained is fluid at room temperature (fuel material section 75). Powdered charcoal 456 for demulsification
This occurs under Article 6.

Example 3 This example involves all the same ingredients as Example 2, but with 6
The difference is that powdered coal with a particle size fraction of 3 microns or more is used.

In this case, 847°6 pieces of charcoal, or 79 pieces of combustible material
% gives a pasty product.

Example 4 In this example, a suspension is obtained by cold mixing of a hot-produced bitumen-water emulsion and pulverized coal. The emulsion of cationic character contains 60% by weight of bitumen, 40% of water, additives of the ``2 lyrum'' type, and hydrochloric acid (total amount of 1 kg K.
The pH of the emulsion should be in the range 2 and 4. The pulverized coal used was from Riedspruit and its has a particle size of 80 microns or less.

This suspension was subjected to a ``physiolysis''-type decomposition test I.
f Implement. The method consists in adding pulverized coal with an average particle size of 400 mfron until a dense paste is obtained (until the suspension breaks down).

At 22 inches the suspension was still in a fluid state, which corresponds to 68.8% of the fuel material suspended in the water.

On the other hand, decomposition was observed with the addition of powdered coal of 25th grade.

Example 5 In this Example 2, a suspension is prepared in the same manner as in Example 4, but the difference is that this suspension is given anionic rather than cationic properties (tall oil use). soda (NaOH) to obtain a pH of 12.3.
) is added.

In this case, the decomposition test showed decomposition with a pulverized coal addition of 17%, which corresponds to a fuel material content of 66.8 wt.

In the example, a paste containing pulverized coal of 63 wt. Obtained by adding at room temperature. The following two types of "fluid" formations were obtained.

Product (a) containing 52% pulverized coal and 10% bitumen, i.e. 62% fuel material and 37% water and additives, 45% pulverized coal and 17.4% bitumen, i.e. 62. Product (b) containing 4% fuel material and 37.6% water and additives.

In conclusion, in order to improve the properties of solid fuel-water-petroleum residue suspensions, the following is desirable.

1) Decrease the lipophilic properties of the carbon, for example by grafting lipophilic-hydrophilic additives onto the powdered coal before mixing and also by manipulating the mixture OpH (lower pH increases the hydrophilic properties of the powdered coal) 2) Increase the hardness of picumen or petroleum distillation residues so as to reduce their adhesion to pulverized coal.

3) Manipulating particle size to increase the powder coal concentration of the product. Especially regarding this point, the pi-mode property f of the existing particle is
! : Improve the degree of filling by increasing (particle size of bitumen or petroleum distillation residues in the emulsion less than 10 microns).

4) Carry out preliminary crushing of the heavy petroleum residues used.

Example 7 A petroleum distillation residue-water emulsion is prepared in the same manner as in Example 1. To this emulsion is added crushed petroleum coke, 75% by weight of which has a particle size of less than 80 microns.

Upon addition of 41.2% petroleum coke, the final product remains fluid (Brookfield viscosity, 15°C, 1
2 r, p, m, (7) LV2 needle: 2ooo
centipoise), total weight of fuel material is 75.0%.

Example 8 A petroleum distillation residue-water emulsion similar to that of Example 1 is intervened. To this emulsion, all pulverized and screened pulverized coal (10,000% by weight of the powder with a particle size of 0 micron or less) is added.

Upon addition of 38.8% pulverized coal, the final product remains fluid (Brookfield viscosity, 15°C, 12r, p,
m LV 2, needle: 900 centipoise)
.

The total weight of fuel material is 70.0 parts.

The same operation is repeated using 100% by weight of demineralized rehydrated powder having a particle size of 40 microns or less. The final mixture obtained has properties similar to those described above.

Example 9 A total crushed petroleum coke-demineralized powder-water mixture is made by mixing the following with stirring:

Demineralized ultra-fine coal. Manufactured from Ermelo type coal. The sulfur content is approximately 0.4%, and the ash content is 3.6%. 90% by weight of it is multi-pulverized petroleum coke with a particle size of less than 17.1 microns.

Sulfur content 2%, ash content 0.8t No. 80t, tchi 80
Micron or less: 44.3
Weight polyhydric: 37.8 Double hereditary Romar D type additive: 0.9% by weight In this way, a stable liquid mixture was obtained, part 10
The viscosity at °C is 1300 centipoise.

The sulfur content of this mixture is less than about 1 part, and the ash content is only about 1 part. Its calorific value is 4800 kcal/kg.

In this way, the present invention is particularly suitable for oil residues! A solid fuel-water-petroleum residue suspension can be produced with a pulverized coal content of 40% and a fuel material content M of the order of 76 when fully used. These products are relatively fluid. By using suitable additives, its stability properties can be adapted to the application.

Among the additives that can be used in the coal-water emulsion mixture, the following emulsifiers can be mentioned.

For cationic emulsions, salts of amines or polyamines; for anionic emulsions, alkaline soaps of fatty acids.

Also, solid fuel - water - petroleum residue 1. Combustion tests conducted on the P/I suspension yielded very good results, including excellent flame characteristics, temperature characteristics, and smoke opacity characteristics. It has a combustion efficiency close to that of coal, and a combustion efficiency close to that of liquid fuels currently in use.

Outgoing representative Boar crotch m France 92,500 Ruilleuma Le Maison Rue du Doct wool gyori 31

Claims (1)

[Claims] 1. Suspension of a powdered solid fuel, such as carbon of mineral chips or products derived from petroleum heavy distillation residues, in an aqueous phase, optionally with at least one additive. In liquid fuels in liquid form, the particle size composition of the powdered solid fuel resulting from grinding, screening operations or demineralization operations is increased by the addition of multiple particle size fractions of products solid at storage temperature resulting from heavy petroleum residues. A liquid fuel according to the present invention, characterized in that the aqueous phase constitutes 15 to 40% by weight of the liquid fuel. 2. Liquid fuel according to claim 1, characterized in that the particle size composition of the powdered solid fuel represents only a part of the particle size composition resulting from a crushing operation, a screening operation or a deashing operation. 3. A liquid fuel according to any one of claims 1 to 3, characterized in that said additional particle size 7 lactose consists of powdered petroleum residue. 4. The powdered petroleum residues are asphaltenes, distillation residues, and/or hydrocracking coke, catalytic cracking coke, coking coke,
and/or combustion residues or distillation residues, and/or
or deasphalted distillation residue, and/or optionally oxidized! A liquid fuel according to any one of claims 1 to 3, characterized in that it is made of bitumen. 5. In the suspension at dC, ultrafine 7 lactations (2
Particle sizes on the order of 80% below 0 microns) consist at least in part of natural or synthetic petroleum residues, such as finely powdered petroleum distillation residues, and suspensions contain between 5 and 70% petroleum residues. and industrial powdered solid fuel from 7o to 5o (
particle size such that 80% by weight have a size below 80 microns), additional moisture and emulsifying and/or stabilizing additives, and the proportion of solids in the final mixture is within the range of 60 to 85 parts. A liquid fuel according to any one of claims 3 to 4. 6. In the mixture of solid fuel-water plus optional additives, said powdered petroleum residue is used as an intermediate particle size fraction, such as a particle size of 1 to 80 microns. Liquid fuel according to any one of items 4 to 4. 7. Powdered petroleum residue with a particle size on the order of 80 to 120 microns is charged to a solid fuel-water fluid mixture containing a small proportion of finely ground solid fuel on the order of 50%. A liquid fuel according to any one of claims 1 to 4, characterized in that: 8. A liquid fuel according to claim 1, characterized in that said additional particle size fraction consists of a petroleum residue emulsion in an aqueous phase. 9. Liquid fuel according to any one of claims 1 to 8, characterized in that the aqueous phase further contains a proportion of an organic solvent, in particular an alcohol such as methanol or ethanol. 10. The petroleum residues are bitumen or deasphalting distillation residues and/or bitumen and/or oxidized pitumen2 and/or atmospheric distillation residues and vacuum distillation residues and/or vis-breaking, catalysts. Claims '$1. Section 8 Section 8 Liquid fuels. 11. A liquid fuel according to claim 8, wherein said emulsion contains up to 75 inches of petroleum residue in water, an emulsifying additive and optionally a cationic or anionic agent. 12. Liquid fuel according to claim 11, characterized in that in the case of cationic emulsions, the emulsifier consists of amine salts or polyamine salts, and in the case of anionic emulsions, the emulsifier consists of alkaline soaps of fatty acids. 13. The liquid fuel according to any one of claims 1 to 12, wherein the solid fuel is natural coal, deashed coal, coal washing machine slime, or petroleum-derived solid fuel. . 14. In order to mix into the composition according to claim 1 together with powdered solid fuel such as natural coal, deashed coal, powdered solid fuel of petroleum origin obtained by crushing or emulsification, solid 414. A method for producing a liquid fuel according to any of claims 1 to 413, characterized in: producing some particle size fraction from a petroleum residue. 15,9 for solid fuel flowable mixtures in asphaltenes, and/or hydrocracking coke, catalytically cracking coke or coking coke, and/or combustion residues or gasification residues and/or oxidized bitumen and/or 15. Process according to claim 14, characterized in that the entire deasphalting distillation residue is added. 16. Process according to claim 5, characterized in that the pulverization of the petroleum residue is carried out cold by mechanical grinding or hot on the liquid phase residue. 17. In the case of hot pulverization, the powdered gold gas can be used to assist, and the subdivided particles are subjected to a rapid cooling process such as quenching with water or quenching with air. Method according to Section 16. 18. The method according to claim 14, characterized in that powdered solid fuel is mixed into the petroleum residue + water + additive emulsion. 19. Mixture consisting of solid fuel, water 2 and additives v! :J
15. A method according to claim 14, characterized in that the petroleum residue + water + optional additive emulsion is completely added to this mixture.